US6288161B1 - Barrier compositions and articles made therefrom - Google Patents
Barrier compositions and articles made therefrom Download PDFInfo
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- US6288161B1 US6288161B1 US08/999,901 US99990197A US6288161B1 US 6288161 B1 US6288161 B1 US 6288161B1 US 99990197 A US99990197 A US 99990197A US 6288161 B1 US6288161 B1 US 6288161B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/17—Articles comprising two or more components, e.g. co-extruded layers the components having different colours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/74—Oxygen absorber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2377/00—Polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/46—Bags
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
- Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2902—Channel shape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- Typical moisture barriers include polyethylene and polypropylene.
- Suitable oxygen barriers include EVOH, PVOH, Nylon and blends thereof. Vinylidene chloride—vinyl chloride copolymers and vinylidene chloride—methyl acrylate copolymers are suitable as both moisture and oxygen barriers.
- barrier materials due to their high cost or their unstable structural characteristics or other weaknesses, it is difficult to fabricate commercial packaging solely out of barrier materials.
- EVOH while having superior oxygen barrier properties, suffers moisture problems because of the many hydroxyl groups in the polymer.
- Other barrier materials are so expensive that to manufacture structures solely from those barriers would be cost prohibitive. Accordingly, it has become a common practice to use multilayer structures, whereby, the amount of expensive or sensitive barrier material may be reduced to a thin layer and an inexpensive polymer can be used on one or both sides of the barrier layer as structural layers.
- the use of multilayer structures permits the barrier layer to be protected from deterioration by structural layers on one or both sides of the barrier layer.
- multilayer structures containing a barrier layer may be cheaper and stronger than a single layer of barrier materials, such structures are more complicated to manufacture than single-layered ones.
- multilayer structures comprised of layers of a variety of different materials may be opposed in some instances on environmental grounds, they may be more difficult to recycle since it is often difficult and expensive to separate the layers.
- reducing the thickness of the barrier layer in a multilayer structure can reduce the barrier properties of the film. Accordingly, there is a need for a single-layer packaging material with suitable barrier properties but without the cost or structural weaknesses of packaging made solely from a barrier material.
- additional multilayer structures having improved barrier properties wherein, the barrier material is reduced to a thinner layer and replaced in part by inexpensive structural layers. These structures have the same barrier properties of prior art barriers but at lower cost due to a decrease in the amount of expensive barrier material used.
- oxygen absorption or oxygen scavenging materials are useful in reducing the amount of oxygen that contaminate the product packaged in the container.
- An example of oxygen scavenging materials and methods of using them is disclosed in U.S. Pat. No. 4,425,410 to Farrell et al, the disclosure of which is hereby incorporated by reference herein.
- Another useful aspect of oxygen absorbing material is that such materials can reduce residual oxygen which is trapped in the headspace of a container during sealing, thereby preventing it from having a deleterious effect on the packaged products.
- PET polyethylene terephthalate resin
- PEN polyethylene naphthalate
- polyesters In order to enhance polyester's gas barrier properties, polyesters have been used in a multilayer structure in combination with a layer having excellent gas barrier properties such as EVOH.
- a layer having excellent gas barrier properties such as EVOH.
- multilayer structures employing polyester, such as PET frequently have adhesion problems between the polyester and the barrier layer which frequently leads to delamination over time.
- One approach to enhancing the gas barrier property of PET is to use a resin mixture which includes PET and a xylylene group containing polyamide resin.
- resin materials are disclosed in U.S. Pat. No. 4,501,781 to Kushida et al.
- One of the considerations encountered with such blends accordingly to Kushida is that there is a limit to the amount of xylylene group-containing polyamide resin that may be present in the PET blend.
- Kushida indicates that amounts of xylylene group-containing polyamide resin greater than 30% by weight causes the container to become a laminated foil structure which is susceptible to exfoliation between the foil layers of the container.
- the permeation of oxygen gas through the walls of a container is less when the container is made wish PET and a xylylene group-containing polyamide than when the container is made solely of PET.
- Kushida reports that a bottle shaped container made with PET-xylylene group-containing polyamide measured 0.0001 cc of oxygen permeation per day compared to 0.0180 cc of oxygen permeation per day for a container made with PET.
- a preferred xylylene group-containing polyamide resin in the present invention is an aromatic polyamide formed by polymerizing meta-xylylene-diamine (H 2 NCH 2 —m—C 6 H 4 —CH 3 NH 2 ) with adipic acid (HO 2 C(CH 2 ) 4 CO 2 H).
- the most preferred such polymer is manufactured and sold by Mitsubishi Gas Chemicals, Japan, under the designation MXD6 or MXD6 nylon.
- the gas barrier property of polyester is enhanced by blending polyester with xylylene group-containing polyamide and a transition metal catalyst.
- Preferred embodiments include blends of PET/MXD6/Cobalt and exhibit superior oxygen barrier and oxygen absorption characteristics that were not present in the prior art structures.
- the structures in this invention are not as clear as the prior art structures.
- Hong discloses that it is believed that the high orientation of the blend increases the surface areas and interface between PET and MXD6 nylon so that there are a greater number of sites at which a reaction or an absorption of oxygen catalyzed by the transition metal catalyst takes place. This increased surface area and interface between PET and MXD6 nylon also causes a change in the refractive characteristics of the materials and results in an increased diffusion of light passing through the structures.
- the disclosures made in the Hong application are hereby incorporated by reference herein.
- FIG. 1 shows a pouch, sealed on three sides and made with the sheet structure of this invention.
- FIG. 2 shows a cross-section of the pouch of FIG. 1 taken at 2 — 2 of FIG. 1 .
- FIG. 3 shows a cross-section of sheet structure used to form the pouch shown in FIGS. 1 and 2 .
- MXD6 nylon oxygen barrier properties of MXD6 nylon are improved by the addition of cobalt octoate and that structures formed from MXD6/cobalt octoate blends and MXD6/cobalt octoate/PET blends have improved clarity and retort characteristics.
- the blends can be made into structures in the form of containers, films, sheets, pouches or lidstock.
- the MXD6/cobalt salt blend and the MXD6/cobalt salt/PET blend can be a single layer film or one layer of a multiple layer film which has been coextruded, extrusion coated or laminated.
- PET is the preferred polyester used in the MXD6/cobalt octoate/polyester blends
- any thermoformable grade polyester with oxygen barrier qualities greater than those of polyolefins can be used.
- cobalt octoate to MXD6 nylon, or to a blend of MXD6 nylon and PET, produces blends that are significantly more impervious to oxygen than structures of MXD6 nylon or MXD6 nylon/PET blends.
- the improved barrier properties of the compositions of the present invention are unaffected by fluctuations of temperature and humidity.
- the oxygen barrier properties of previously known barrier polymers such as EVOH are adversely affected at 100% relative humidity (RH) and so they must be protected by a moisture barrier polymer.
- cobalt octoate in an amount of up to about 250 ppm to a xylylene group-containing polyamide, preferably MXD6, or a xylylene croup containing polyamide and polyester (preferably PET) blend produces a blend that does not require protection from 100% RH and thus, eliminates the need for a moisture barrier layer.
- Structures containing PET/MXD6/Cobalt octoate blends or MXD6/cobalt octoate blends known in the art are oriented to increase oxygen barrier and oxygen absorption. However, such orientation may have a deleterious effect on the color and clarity of the structure. These problems are caused by a change in the refractive index of the materials when the polymers are oriented. Orientation enlarges the domain size of MXD6 so that it is greater than the wavelength of light and this results in the increased scattering of light. See Table 1.
- the oxygen barrier and oxygen absorbing compositions of the present invention can also be formed into multiple layer structures.
- These multiple layer structures have a core layer of either a MXD6 nylon/cobalt octoate blend or a MXD6 nylon/polyester/cobalt octoate blend disposed between two adjacent layers.
- the two adjacent layers are comprised of either a polyester or a polyamide.
- one adjacent layer can be a polyester and the other adjacent layer can be a polyamide.
- the polyester is PET and the polyamide is nylon 6 .
- these structures are orientated to a degree so that the MXD6 domain increases in size up to less than the wavelength of light.
- any themoformable grade polyester with oxygen barrier qualities greater than those of polyolefins can be used to form clear packages and containers with almost zero oxygen permeability when blended with MXD6 and cobalt octoate. It has been discovered that the problem of haze is solved by extrusion blow molding the blend when it is in a molten state. This minimizes the orientation that occurs when the packages or containers are fabricated. By limiting the orientation, the domain sizes of the polyester and MXD6 do not increase to where they are greater than the wavelength of light and diffusion occurs.
- Table 2 shows a comparison of the amount of haze in bottles produced by extrusion blow molding and injection reheat blow molding.
- the extrusion blow molded bottles display a significant reduction in the percent haze.
- Cast films were prepared using Selar polyester which was blended with MXD6 nylon with and without the addition of cobalt octoate. In the presence of MXD6, these films showed a mild grey color. However, when these films were thermoformed, clear structures were produced. Moreover, haze was significantly reduced by minimizing the degree of orientation. Table 3 shows the normalized % haze/mil of materials compared to haze in injection-reheat blow molded bottles.
- the composition of the present invention also comprises a blend of polyester, such as PET, and up to about 30% of a barrier material, such as a xylylene group-containing polyamide with about 49 ppm to about 110 ppm catalyst, most preferably in the form of a nascent catalyst residue from the PET.
- the barrier material is preferably a xylylene group-containing polyamide resin commonly known as MXD6 nylon which is available from Toyobo or Mitsubishi Gas Chemicals Company.
- the PET is available from Eastman Hoechst Celanese, ICI America, Shell Chemical or DuPont.
- the catalyst is a transition metal. Cobalt has been found to be particularly useful in the present invention. Transition metal catalysts are defined as catalyses of metals which have filled or partially filled outer “d” orbitals or are those having filled “d” orbitals and filled or partially filled “p” orbitals.
- Multi-layer structures having a barrier layer of MXD6 nylon and two outer layers of PET wherein the MXD6 nylon comprises about 10 wt. % of the total structure will provide a clear film or container.
- the oxygen barrier properties of such multilayer structures are not as good as blends of the present invention.
- such multilayer structures will not provide the oxygen absorption capabilities of the present invention.
- a physical blend of the pellets be made in a suitable mixing device.
- the process disperses the particles of the barrier material in the polyester.
- PET, MXD6 nylon and cobalt salt are mixed together in a screw extruder to form a blend. This extrusion is then oriented to a limited degree by extrusion blow-molding to form a structure such as a container or bottle.
- the barrier material is normally present as spherical particles dispersed in PET.
- Containers made in accordance with this method are clear, unlike the prior art structures described above. However, these containers exhibit the same superior oxygen barrier and oxygen absorption characteristics of the prior art structures disclosed by Hong.
- a blend consisting of PET, up to about 30 wt. % MXD6 nylon (preferably up to 10 wt. % MXD6 nylon) and up to about 110 ppm cobalt salt is coextruded as a barrier layer with a layer of PET on each surface thereof to form a three layer structure.
- the barrier layer would be a blend of 10 wt. % MXD6 nylon and the overall percentage of MXD6 nylon in the structure would be about 2 wt. %.
- Containers made from this structure are clear and do not exhibit the haze found in prior art containers.
- the catalyst in the blends of the present invention improves the barrier properties of structures made therefrom by providing oxygen absorption capabilities.
- compositions of blends of a xylylene group—containing polyamide and up to 250 PPM of a transition metal catalyst do not have their oxygen barrier characteristics adversely affected by the high relative humidity conditions experienced during retort. Therefore, they can be used to form films that do not require additional moisture barrier layers.
- the preferred blends of these compositions are comprised of MXD6 and cobalt octoate and they are used to form the oxygen barrier layer of a single or multiple layer film.
- the barrier layer is disposed between two adjacent layers.
- One, or both, of the adjacent layers is comprised of a polyester or a polyamide.
- the preferred polyester is PET and the preferred polyamide is nylon 6.
- these compositions are oriented to a degree so that the MXD6 domain increases in size up to less than the wavelength of light.
- FIG. 1 illustrates a pouch such as is the desired packaging structure of one of the embodiments of this invention.
- a cross-section of a portion of the pouch is shown in FIG. 2 .
- the sheet material used to make the pouch is seen in FIG. 3 .
- the FIG. 2 construction consists of two sheet elements of the FIG. 3 construction in face to face relation with the layers 12 joined at the one edge in a heat seal.
- the pouch is formed by arranging the two sheet elements in face to face relationship and forming heat seals 19 about the common periphery.
- the pouch may be formed by folding a sheet element onto itself and forming heat seals about the edges. Either way the formed pouch appears as shown in FIG. 1 .
- layer 12 is a heat sealable layer comprised of a polyester or a polyamide.
- Layer 14 is an optional adhesive, or tie layer, selected based on the materials in the adjacent layers.
- Layer 16 a blend of a xylylene group-containing polyamide and up to 250 ppm of a transition metal catalyst.
- Layer 18 is also an optional adhesive, or tie, layer and is also selected based on the materials in the adjacent layers.
- Layer 20 is an outer protective layer comprised of a polyester or a polyamide.
- the formed pouch is intended for packaging products which are subjected to a sterilizing process after the product is in the package and the package is sealed.
- a common sterilizing process is known as autoclave, or retort, processing.
- closed and sealed packages are placed in a pressure vessel. Steam and water are then introduced into the vessel at about 275° F. at a sufficiently high pressure to permit maintenance of the desired temperature. The temperature and pressure are usually maintained for about 30 minutes. Finally, the pressure vessel is cooled and the pressure temporarily maintained until the packages cool internally. Finally the pressure is released and the processed packages are removed.
- Sheet structures of this invention generally range in thickness from about 3 mils up to about 10 mils.
- the thickest layer is usually the sealant layer and the thinnest layers usually are the tie layers and the oxygen barrier layer.
- the sheet structures of this invention may be made by conventional processes and combinations of processes.
- the process and its sequences may be selected according to the equipment and polymers available.
- the specific structure selected and the compositions of the oxygen barrier layer and the outer layers of polyester will be at least partially dependent on the process and its sequences.
- concentrations of about 49 ppm to about 120 ppm residual catalyst in a polyester-barrier material blend have not only superior oxygen barrier properties but also significant oxygen scavenging capabilities.
- compositions having superior oxygen barrier and oxygen absorption characteristics may be employed as a mono or multilayer film, such as, for example, in a pouch or flexible lidstock. These compositions may also be formed into rigid containers or may comprise the sidewall, body, lid or entire container. Also, the composition of the present invention may be formed into a chip and used in a container as an oxygen scavenger.
- a preferred embodiment of the present invention is a blend of PET and MXD6 nylon, wherein the MXD6 nylon is present in an amount of from about 2.5 weight a to about 15 weight % with the balance being PET. Cobalt is present in a range of 49 ppm to about 120 ppm with 62 ppm being most preferable. Another embodiment is pure MXD6 with between 49 and 120 ppm cobalt.
- the MXD6 nylon is present in an amount of from about 4 weight % to about 10 weight % with the balance being PET.
- Cobalt is preferably present in the range of from about 49 ppm to about 120 ppm and most preferably present in an amount of about 62 ppm.
- MXD6 nylon is present in the blend in an amount of about 7.5% with the remainder being PET and cobalt, present in the amounts stated above.
- nascent cobalt is present as a residual of the PET polymerization catalyst.
- Specially added cobalt is preferably present as a cobalt salt dispersed in mineral spirits such as that sold under the trademark Nuodex by Huls America.
- the Nuodex products contain up to about 15% by weight cobalt.
- the preferred maximum amount of catalyst is about 250 ppm and is dependent on the structure being formed from the PET/MXD6/cobalt blends.
- the xylylene group containing polyamide is preferably a MXD6 nylon which is produced by condensation polymerization of metha-xylylene diamine (MXDA) and adipic acid.
- MXDA metha-xylylene diamine
- the degree of orientation not exceed the limit at which the refractive characteristics of the blend materials change and the clarity of the structures deteriorates.
- the multiple layer sheet structures have outer layers comprised of polyesters or polyamides that are suitable for heat sealing.
- an adhesive layer is disposed on one or both sides of the barrier blend layer to bond the polyester or polyamide layers to the blend layer.
- One of the embodiments of the present invention relates to the improvement in the clarity of polyester/xylylene group containing polyamide blend bottles through a change in the process rather than a change in the materials used.
- the preferred blends are comprised of PET and MXD6 nylon. It is known in the art that the color in PET/MXD6 structures is due to the presence of catalyst residue in the polyester. This color can be controlled by limiting the amount of catalyst. Also, the orientation of PET and MXD6 during the manufacturing process (two stage injection—reheat blow molding) results in the development of haze caused by refractive index changes and the enlarged domains of MXD6.
- the present invention provides a solution to the problems of color and haze by using the extrusion blow-molding process and extrudable polyester.
- the preferred polyester is PET.
- extrusion blow molding the bottle is produced when the polymer is in its molten state and therefore, the orientation is minimized. It is believed that the domain size of the unoriented MXD6 is less than the wavelength of light and :he refractive indices of PET and MXD6 are nearly the same. Thus, light passing through unoriented MXD6 structures does not scatter and produce haze.
- polyester/MXD6/cobalt blend is disposed between two polyester layers.
- the preferred polyester is PET.
- the cobalt octoate is present in an amount of up to 250 ppm.
- the preferred amount is 120 ppm.
- cast films consisting of MXD6 nylon and 250 ppm cobalt octoate were prepared in thicknesses from 5 to 35 mils and were tested for oxygen permeations against cast films of MXD6 nylon without cobalt octoate.
- the results shown below in Table 4 demonstrate the improved oxygen barrier characteristics of films of MXD6 nylon and cobalt octoate.
- a three layer structure of the present invention having outer layers of PET and a core layer of MXD6 nylon/100 ppm cobalt octoate blend (wherein the core layer comprised 10% of the structure) was used to produce bottles on a Nissei stretch blow molding machine. Other bottles were produced by the same means and from similar material except the core layer did not contain cobalt. After the bottles were aged for three months at 0% relative humidity, they were tested for oxygen permeation. The results are shown below in table 5.
- Flexible lidstock or pouches can be formed from coextruded film structures in accordance with the present invention having a core layer of a blend of MXD6 nylon and cobalt octoate disposed between two layers of nylon 6.
- the film was tested before and after retort for oxygen permeation at test conditions of 100% oxygen, 0% relative humidity (RH) and at 100% oxygen, 100% RH. The results are shown below in tables 6 and 7.
Abstract
Description
TABLE 1 |
THE EFFECT OF REFRACTIVE INDEX AND PARTICLE |
SIZE ON HAZE |
ORIENTA- | REFRAC- | NORMALIZED | ||
TION | TIVE | INDEX | PARTICLE | BLEND HAZE |
DRAWDOWN | MXD 6 | PET | SIZE (μm) | (% HAZE/MIL) |
0 | 1.580 | 1.578 | 0.1-0.3 | 0.2 |
9 | 1.589 | 1.620 | 2-4 | 0.8 |
TABLE 2 |
COMPARISON OF THE HAZE OF INJECTION BLOW MOLDED |
AND EXTRUSION BLOW MOLDED BOTTLES |
NORMALIZED HAZE | |||
BOTTLES | (% HAZE/MIL) | ||
INJECTION - REHEAT | 3.16 | ||
BLOW MOLDED | |||
EXTRUSION BLOW | 0.2 | ||
MOLDED - MATTE | |||
FINISH MOLD | |||
EXTRUSION BLOW | 0.12 | ||
MOLDED - POLISHED MOLD | |||
TABLE 3 |
MEASUREMENTS OF % HAZE/THICKNESS (% HAZE/MIL) |
Cast Film Formed Into | Injection-Blow | ||
Cast Film | Thermoformed Meat | Molded Bottles | |
Material | Unoriented | Packages | Oriented |
Selar PT207 | 0.2 | 0.18 | 0.16 |
Selar PT207 + | 0.25 | 0.3 | 3.16 |
7.5% MXD6 + | |||
120 PPM Cobalt | |||
TABLE 4 | |||
oxygen permeation (ccmil/m*2 day) | |||
thickness | (green cast films at 0% RH) |
Variable | (mils) | 36 (hrs) | 84 | 180 | 276 | 324 | ||
I. | MXD6 film | 5 | 17 | 15 | 5 | 11 | 12 |
9 | 15 | 13 | 9 | — | — | ||
19 | 30 | 12 | 12 | — | — |
32 | 93 | 38 | 13 | 7 | 12 | ||
II. | MXD6 film + | ||||||
250 ppm | 5 | 8 | 3 | 1 | 0.3 | 0.5 |
Co | 11 | — | 0 | 0 | — | — |
19 | 23 | 1 | 0 | — | — | ||
35 | 39 | 0 | 0 | — | — | ||
TABLE 5 | ||||
thickness | oxygen permeation | |||
Variables | (mils) | (ccmil/m* 2 day) | ||
(1) | PET/MXD6/PET | 27 | 42 |
(2) | PET/MXD6 + 100 ppm Co/PET | 28 | 9 |
*Oxygen barrier is normalized by total thickness. not by barrier thickness |
TABLE 6 |
(TEST CONDITIONS: 100% OXYGEN; 0% RH; |
UNAGED SAMPLE) |
TOTAL | STEADY STATE | |
THICKNESS | PERMEATION | |
SAMPLE | (MILS) | RATE* |
POST RETORT NYLON 6/1 MIL | 3.53 | 6.2 |
MXD6+120 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/2 MIL | 4.44 | 0.1 |
MXD6+120 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/2 MIL | 4.74 | 0.1 |
MXD6+120 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/1 MIL | 3.31 | 0.6 |
MXD6+250 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/1 MIL | 3.38 | 3.2 |
MXD6+250 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/2 MIL | 4.50 | 0.0 |
MXD6+250 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/2 MIL | 4.84 | 0.0 |
MXD6+250 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6 | 3.14 | 48.0 |
POST RETORT NYLON 6 | 2.88 | 39.4 |
*CC/SQ M · DAY · ATM |
TABLE 6 |
(TEST CONDITIONS: 100% OXYGEN; 0% RH; |
UNAGED SAMPLE) |
TOTAL | STEADY STATE | |
THICKNESS | PERMEATION | |
SAMPLE | (MILS) | RATE* |
POST RETORT NYLON 6/1 MIL | 3.53 | 6.2 |
MXD6+120 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/2 MIL | 4.44 | 0.1 |
MXD6+120 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/2 MIL | 4.74 | 0.1 |
MXD6+120 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/1 MIL | 3.31 | 0.6 |
MXD6+250 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/1 MIL | 3.38 | 3.2 |
MXD6+250 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6/2 MIL | 4.50 | 0.0 |
MXD6+250 PPM Co/NYLON 6 | ||
POST RETORT NYLON 6/2 MIL | 4.84 | 0.0 |
MXD6+250 PPM Co/NYLON 6 | ||
PRE RETORT NYLON 6 | 3.14 | 48.0 |
POST RETORT NYLON 6 | 2.88 | 39.4 |
*CC/SQ M · DAY · ATM |
Claims (34)
Priority Applications (2)
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US08/999,901 US6288161B1 (en) | 1990-01-31 | 1997-12-24 | Barrier compositions and articles made therefrom |
US09/453,782 US6239210B1 (en) | 1990-01-31 | 1999-12-03 | Barrier compositions and articles made therefrom |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US07/472,400 US5281360A (en) | 1990-01-31 | 1990-01-31 | Barrier composition and articles made therefrom |
US14266393A | 1993-10-25 | 1993-10-25 | |
US08/999,901 US6288161B1 (en) | 1990-01-31 | 1997-12-24 | Barrier compositions and articles made therefrom |
Related Parent Applications (1)
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US14266393A Continuation | 1990-01-31 | 1993-10-25 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US09/453,782 Division US6239210B1 (en) | 1990-01-31 | 1999-12-03 | Barrier compositions and articles made therefrom |
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US6288161B1 true US6288161B1 (en) | 2001-09-11 |
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US09/453,782 Expired - Lifetime US6239210B1 (en) | 1990-01-31 | 1999-12-03 | Barrier compositions and articles made therefrom |
Family Applications After (1)
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US09/453,782 Expired - Lifetime US6239210B1 (en) | 1990-01-31 | 1999-12-03 | Barrier compositions and articles made therefrom |
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US (2) | US6288161B1 (en) |
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